US6045869A - Water-insoluble hydrophilic marine coating and methods - Google Patents
Water-insoluble hydrophilic marine coating and methods Download PDFInfo
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- US6045869A US6045869A US09/238,818 US23881899A US6045869A US 6045869 A US6045869 A US 6045869A US 23881899 A US23881899 A US 23881899A US 6045869 A US6045869 A US 6045869A
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- 239000002519 antifouling agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
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- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 229920003986 novolac Polymers 0.000 claims abstract description 4
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- 150000002576 ketones Chemical class 0.000 claims abstract description 3
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- 239000011787 zinc oxide Substances 0.000 claims description 7
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- 239000000049 pigment Substances 0.000 claims description 3
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- 239000005751 Copper oxide Substances 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
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- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
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- 239000012736 aqueous medium Substances 0.000 claims 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000446 fuel Substances 0.000 abstract description 13
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- 229920000642 polymer Polymers 0.000 abstract description 4
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- 239000011152 fibreglass Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- XQMVBICWFFHDNN-UHFFFAOYSA-N 5-amino-4-chloro-2-phenylpyridazin-3-one;(2-ethoxy-3,3-dimethyl-2h-1-benzofuran-5-yl) methanesulfonate Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1.C1=C(OS(C)(=O)=O)C=C2C(C)(C)C(OCC)OC2=C1 XQMVBICWFFHDNN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
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- 230000003068 static effect Effects 0.000 description 2
- BCCGKQFZUUQSEX-WBPXWQEISA-N (2r,3r)-2,3-dihydroxybutanedioic acid;3,4-dimethyl-2-phenylmorpholine Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O.OC(=O)[C@H](O)[C@@H](O)C(O)=O.O1CCN(C)C(C)C1C1=CC=CC=C1 BCCGKQFZUUQSEX-WBPXWQEISA-N 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 241001523707 Balanidae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
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- 241000237536 Mytilus edulis Species 0.000 description 1
- NTNWOCRCBQPEKQ-UHFFFAOYSA-N NG-mono-methyl-L-arginine Natural products CN=C(N)NCCCC(N)C(O)=O NTNWOCRCBQPEKQ-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000131858 Siboglinidae Species 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
Definitions
- the present invention relates to surface coatings, and, more particularly, to such coatings for use in a marine environment.
- Marine coatings for application to moving watercraft and static underwater structures are known for use to preserve surfaces, improve their appearance, and reduce drag for moving watercraft.
- Such watercraft may comprise, but are not intended to be limited to, movable boats such as sailboats, yachts, inboard and outboard motor boats, rowboats, motor launches, canoes, kayaks, waterskis, surfboards, sailboards, waterbikes, ocean liners, tugboats, tankers, cargo ships, submarines, aircraft carriers, pontoons for sea planes, and destroyers.
- Underwater static structures may include, but are not intended to be limited to, wharves, piers, pilings, bridges, and other structures that may comprise wood, metal, plastic, fiberglass, glass, or concrete.
- Antifouling compositions have also been known to be used against such organisms as barnacles, algae, slime, acorn shells (Balanidae), goose mussels (Lepodoids), tubeworms, sea moss, oysters, brozoans, and tunicates.
- Coatings may be hydrophilic or hydrophobic, the latter incurring friction between the moving surface and the water and including Teflon-like, paraffin wax, and fluorocarbon/silicone materials.
- the former maintains an adhering layer of water, the kinematic friction occurring with the water through which the craft moves.
- An additional object is to provide a composition and method for improving fuel efficiency in marine craft.
- compositions and methods for coating marine watercraft having the property of reducing kinematic friction comprises a polymer comprising a polyhydroxystyrene of the novolak type.
- composition further comprises an antifouling agent.
- a first embodiment of the method of the present invention comprises applying the composition as described above to an outer surface of a marine watercraft to achieve a coating thereof.
- the composition is applied in a solution in an appropriate solvent, which may comprise a low-molecular-weight oxygenated hydrocarbon such as an alcohol or ketone.
- an appropriate solvent which may comprise a low-molecular-weight oxygenated hydrocarbon such as an alcohol or ketone.
- the coated surface is smooth and free of tackiness and thus is not fouled by common water debris such as sand and weeds.
- the coating is insoluble in water and resists abrasion, giving a functional lifetime that has been estimated to be a few years of continuous use.
- a second embodiment comprises a method for increasing the kinematic efficiency of a marine watercraft, including applying the composition to a submersible surface of a marine watercraft.
- a third embodiment comprises a method for making the composition, including blending the polyhydroxystyrene in a low-molecular-weight oxygenated hydrocarbon solvent.
- composition of the present invention results in a hydrophilic surface having a considerably reduced contact angle.
- the contact angle is reduced to about 15°.
- the use of the coating is beneficial on watercraft to increase the speed thereof and/or to improve the fuel utilization.
- FIGURE illustrates the laboratory apparatus used to test the effect of the coating of the present invention upon the speed of an object falling through water.
- a preferred embodiment of the composition comprises polyhydroxystyrene dissolved in methanol as a 5-20 wt/vol % solution and an antifouling agent also present at 5-10 wt/vol %.
- the antifouling agent comprises at least one compound selected from the group consisting of copper powder, copper oxide, zinc oxide (Kadox 911), titanium oxide (Degussa P-25), and tin oxide.
- a pigment may also be included.
- a copolymerization of the polyhydroxystyrene with at least one other hydroxylated polymer such as polyhydroxylethylmethacrylate and polyhydroxymethylene or with another hydrophilic polymer such as polyallylamine, polyaminostyrene, polyacrylamide, or polyacrylic acid allows a variation of the coating without reducing the solubility of the copolymer in the solvent, while also not increasing the solubility of the dry coated polymer in water.
- a laboratory apparatus 10 used to test the effectiveness of the coating of the present invention on a plastic bob 12 to affect the speed with which the bob 12 drops 1.3 m through sea water under the influence of gravity.
- An exemplary bob 12 comprises a plastic hydrophobic pointed cylinder approximately 1.26 cm in diameter and from 7.62 to 25.40 cm in length.
- the apparatus 10 includes a glass tube 14 1.52 m long and having an inner diameter of 3.5 cm filled with artificial seawater 11.
- the bob 12 was allowed to fall from an initial position 20 to a second position 22 1.3 m apart.
- a photoelectric detector 16 at the initial position 20 starts a digital electronic timer 18.
- a second photoelectric detector 24 at the second position 22 stops the timer 18.
- the time recorded typically in the second range, depending upon the size and mass of the falling bob 12, represents the time taken for the bob 12 to fall from the initial position 20 to the second position 22.
- the bob 12 also has a thread 26 attached to its top end, which enables the bob 12 to be raised after resetting the timer 18 to ready it for another test.
- the initial position 20 should be set carefully in order to achieve reproducible results with a low standard deviation from the mean when ten identical, or as close to identical as possible, tests are averaged.
- the coating was also applied to a test boat having an onboard computer to monitor the power, speed, and rpm.
- the characteristics of this exemplary test boat are given in Table 3, and the results of three tests under different conditions of speed and rpm for the uncoated and coated boat are given, respectively, in Tables 4A and 4B, with a summary given in Table 5.
- the coating effected an increase in speed of 8%, and the fuel savings was approximately 10% when the boat was fully in the water, i.e., prior to planing.
- the coated boat tended to plane at lower throttle speed and felt more slippery in the water than the uncoated boat.
- composition and methods of the present invention represent a significant increase in speed and fuel efficiency, thus conferring concomitant ecological and economic benefits.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The composition for coating marine watercraft has the property of reducing kinematic friction and includes a polymer comprising a polyhydroxystyrene of the novolak type. In a preferred embodiment the composition further comprises an antifouling agent. One of the methods entails coating an outer surface of a marine watercraft with the composition. Preferably the composition is applied in a solution in an appropriate solvent, for example, a low-molecular-weight oxygenated hydrocarbon such as an alcohol or ketone. The coated surface is smooth and free of tackiness and thus is not fouled by common water debris such as sand and weeds. The coating is insoluble in water and resists abrasion, giving a functional lifetime that has been estimated to be a few years of continuous use. An application of the composition of the present invention to a water-submersible surface results in a hydrophilic surface having a considerably reduced contact angle. Thus the use of the coating is beneficial on watercraft to increase the speed thereof and/or to improve the fuel utilization.
Description
1. Field of the Invention
The present invention relates to surface coatings, and, more particularly, to such coatings for use in a marine environment.
2. Description of Related Art
Marine coatings for application to moving watercraft and static underwater structures are known for use to preserve surfaces, improve their appearance, and reduce drag for moving watercraft. Such watercraft may comprise, but are not intended to be limited to, movable boats such as sailboats, yachts, inboard and outboard motor boats, rowboats, motor launches, canoes, kayaks, waterskis, surfboards, sailboards, waterbikes, ocean liners, tugboats, tankers, cargo ships, submarines, aircraft carriers, pontoons for sea planes, and destroyers. Underwater static structures may include, but are not intended to be limited to, wharves, piers, pilings, bridges, and other structures that may comprise wood, metal, plastic, fiberglass, glass, or concrete.
Some coatings known in the art include those described in U.S. Pat. Nos. 3,575,123; 5,488,076; and 5,554,214. Antifouling compositions have also been known to be used against such organisms as barnacles, algae, slime, acorn shells (Balanidae), goose mussels (Lepodoids), tubeworms, sea moss, oysters, brozoans, and tunicates.
Coatings may be hydrophilic or hydrophobic, the latter incurring friction between the moving surface and the water and including Teflon-like, paraffin wax, and fluorocarbon/silicone materials. The former maintains an adhering layer of water, the kinematic friction occurring with the water through which the craft moves.
It is therefore an object of the present invention to provide a method of reducing kinematic friction between a marine watercraft and the water through which the watercraft moves.
It is an additional object to provide a coating for a marine watercraft for reducing kinematic friction.
It is a further object to provide such a coating that is hydrophilic.
It is another object to provide such a coating that also possesses antifouling properties.
It is yet an additional object to provide a new use for a novolak-type polymeric composition.
An additional object is to provide a composition and method for improving fuel efficiency in marine craft.
These objects and others are attained by the present invention, a composition and method for coating marine watercraft having the property of reducing kinematic friction. The composition comprises a polymer comprising a polyhydroxystyrene of the novolak type. In a preferred embodiment the composition further comprises an antifouling agent.
A first embodiment of the method of the present invention comprises applying the composition as described above to an outer surface of a marine watercraft to achieve a coating thereof. Preferably the composition is applied in a solution in an appropriate solvent, which may comprise a low-molecular-weight oxygenated hydrocarbon such as an alcohol or ketone. The coated surface is smooth and free of tackiness and thus is not fouled by common water debris such as sand and weeds. The coating is insoluble in water and resists abrasion, giving a functional lifetime that has been estimated to be a few years of continuous use.
A second embodiment comprises a method for increasing the kinematic efficiency of a marine watercraft, including applying the composition to a submersible surface of a marine watercraft.
A third embodiment comprises a method for making the composition, including blending the polyhydroxystyrene in a low-molecular-weight oxygenated hydrocarbon solvent.
An application of the composition of the present invention to a water-submersible surface results in a hydrophilic surface having a considerably reduced contact angle. For example, when the composition is applied to a fiberglass/polyester surface with an initial contact angle of approximately 60° with water as determined by the tilting plate method (see N. K. Adam, The Physics and Chemistry of Surfaces, Oxford Univ. Press, 1941), the contact angle is reduced to about 15°. Thus the use of the coating is beneficial on watercraft to increase the speed thereof and/or to improve the fuel utilization.
The features that characterize the invention, both as to organization and method of operation, together with further objects and advantages thereof, will be better understood from the following description used in conjunction with the accompanying drawing. It is to be expressly understood that the drawing is for the purpose of illustration and description and is not intended as a definition of the limits of the invention. These and other objects attained, and advantages offered, by the present invention will become more fully apparent as the description that now follows is read in conjunction with the accompanying drawing.
THE FIGURE illustrates the laboratory apparatus used to test the effect of the coating of the present invention upon the speed of an object falling through water.
A description of the preferred embodiments of the present invention will now be presented with reference to the FIGURE.
A preferred embodiment of the composition comprises polyhydroxystyrene dissolved in methanol as a 5-20 wt/vol % solution and an antifouling agent also present at 5-10 wt/vol %. The antifouling agent comprises at least one compound selected from the group consisting of copper powder, copper oxide, zinc oxide (Kadox 911), titanium oxide (Degussa P-25), and tin oxide. A pigment may also be included.
A copolymerization of the polyhydroxystyrene with at least one other hydroxylated polymer such as polyhydroxylethylmethacrylate and polyhydroxymethylene or with another hydrophilic polymer such as polyallylamine, polyaminostyrene, polyacrylamide, or polyacrylic acid allows a variation of the coating without reducing the solubility of the copolymer in the solvent, while also not increasing the solubility of the dry coated polymer in water.
Test Apparatus
A laboratory apparatus 10 used to test the effectiveness of the coating of the present invention on a plastic bob 12 to affect the speed with which the bob 12 drops 1.3 m through sea water under the influence of gravity. An exemplary bob 12 comprises a plastic hydrophobic pointed cylinder approximately 1.26 cm in diameter and from 7.62 to 25.40 cm in length.
The apparatus 10 includes a glass tube 14 1.52 m long and having an inner diameter of 3.5 cm filled with artificial seawater 11. The bob 12 was allowed to fall from an initial position 20 to a second position 22 1.3 m apart. A photoelectric detector 16 at the initial position 20 starts a digital electronic timer 18. A second photoelectric detector 24 at the second position 22 stops the timer 18. The time recorded, typically in the second range, depending upon the size and mass of the falling bob 12, represents the time taken for the bob 12 to fall from the initial position 20 to the second position 22.
The bob 12 also has a thread 26 attached to its top end, which enables the bob 12 to be raised after resetting the timer 18 to ready it for another test. The initial position 20 should be set carefully in order to achieve reproducible results with a low standard deviation from the mean when ten identical, or as close to identical as possible, tests are averaged.
Exemplary Test Results
Tests undertaken on the apparatus described above have shown that the falling time, which ranges from 1.5 to 6 sec depending upon the size and mass of the object, decreases by 100-300 msec when a coating of the present invention has been applied (Table 1).
TABLE 1
______________________________________
Contact angles of water on various surfaces before
and after coating with a solution of Polyhydroxystyrene
Surface Contact Angle Before
Contact Angle after
______________________________________
Polyethylene
56 16
Stainless Steel
42 20
61 18
Aluminum 70 15
Fiberglass/polyester
53 22
60 17
Silicone rubber
48 18
Plexiglass 60 12
63 14
Polystyrene 58 15
Wood (oak) 33 18
______________________________________
This represents an improvement in the speed of 2-8%. The maximum speed at which these tests were performed correspond to the equivalent of about 2.5 knots. This is far below the 9-20 knots of ocean tankers or the 20-30 knots of passenger ships and ocean cargo vessels. However, the results of Table 2(b) show that the degree of improvement of the coating increases as the speed of the moving object increases for a fixed suface-to-water contact area.
It has been shown that an application of a 5-20% solution of polyhydroxystyrene in methanol changes a hydrophobic surface into a hydrophilic one. The contact angle of flat metal, plastic, and wood surfaces were determined by the tilting plate method before and after application of the coating. The results are given in Table 2, where the contact angles are the averages of the advancing and receding angles. These data show that the coating causes a significant decrease in the contact angle of water with the surface. Similar data obtain when an antifouling agent such as listed previously.
TABLE 2
______________________________________
Some typical results showing (a) the effect polyhydroxystyrene
coatings on bobs of various materials by a determination of the time
for the bob to fall (in milliseconds, ms), and (b) the effect
of speed on the improvement due to the coatings for a fixed
______________________________________
surface.
Anti- Time (ms)
Time (ms)
Percentage
fouling Before After Improve-
(a) Material* Agent Coating Coating ment
______________________________________
1. Polyethylene
ZnO 3869.4 ± 44
3567.0 ± 30
7.9%
2. Nylon None 4283 ± 79
4179 ± 41
2.4%
3. Nylon ZnO 3098.2 ± 26
2988 ± 27
3.5%
4. Polyvinylchloride
ZnO 4561 ± 38
4404 ± 34
3.4%
5. Polyvinylchloride
None 1519.3 ± 13
1489.0 ± 10
2.0%
______________________________________
Mass of Bob
Time (ms) Time (ms)
Percentage
(b) Grams Before Coating
After Coating
Improvement
______________________________________
6. 32.9 5047.6 ± 56
4959 ± 72
1.8%
7. 34.2 2011.7 ± 27
1947.6 ± 20
3.2%
8. 38.3 1711.3 ± 21
1664.4 ± 12
6.0
______________________________________
*1 & 3 were in distilled water with ZnO at 10% wt/vol %. All others were
in sea water.
4 ZnO was at 15 wt/vol %.
6, 7, 8 the bob was a hollow polymethylmethacrylate pointed cylinder to
which weights were added to make the bob fall faster.
The coating was also applied to a test boat having an onboard computer to monitor the power, speed, and rpm. The characteristics of this exemplary test boat are given in Table 3, and the results of three tests under different conditions of speed and rpm for the uncoated and coated boat are given, respectively, in Tables 4A and 4B, with a summary given in Table 5. For fixed power, the coating effected an increase in speed of 8%, and the fuel savings was approximately 10% when the boat was fully in the water, i.e., prior to planing. The coated boat tended to plane at lower throttle speed and felt more slippery in the water than the uncoated boat.
TABLE 3 ______________________________________ Boat Characteristics ______________________________________ GasTest Number Test 1Boat Model 26 Nova SpyderBoat Number WELP 340 E788 Engine Manufacturer Mercruiser Twin Engine Model 350 Magnum Stem Drive Model Alpha One Gear Ratio (X:1) 1.50:1Propshaft Hp 500 StbdIdle Timing 8 Degrees BTDC PortIdle Timing 8 Degrees BTDC Stbd Adv Timing 32 Degrees BTDC Port Adv Timing 32 Degrees BTDC Rpm Range 4400-4800 RPM X"Dimension 51/4 (11/4" Above) Fuel Load 60.0Gallons 4900 LbsAft Fuel Capacity 120Gallons 2800 Lbs Fwd Boat Weight atTest 9011Pounds 7700 Lbs Ttl Center of Gravity 104.7 Inches 24.00 Ft. Dist.Trim Tabs Bennett 9" × 12" (Performance) Exhaust System Thru-transom 100 Pounds GearDriver Willie Petrate 200 Pounds Passengers Don, Ken, Lee 640 Pounds Location Sarasota Bay Water Conditions Lite Chop Wind Conditions Northwest @ 10 MPH Radar Stalker Fuel Flow Meter Floscan 7000 G" Meter Vericom 2000r Propeller Model Quicksilver Prop Material Stainless Steel Wellcraft PN 1405==== Manufacturer's PN 48-163184 Number of Blades Three Rh Diameter 133/4"Pitch 21" True Pitch 22.0 Inches Hull Constant 280,6633 Minimum Rpm to Maintain Plane 2400 RPM Boat Position Angle atRest 4 Degrees Boat List Angle atRest 0 Degrees Bow Measurement (Inches) N/A Inches Transom Measurement (Inches) N/A Inches NMMA Boat Maneuverability Test OK Backdown Test Use Caution Sight Anti-ventilation Plate Well Defined Total Fuel this Test 12.0 Gallons Total Engine Time this Test One Hour RecommendedCruising Rpm 3500 RPM Acceleration Test Test Seconds Feet Time to plane 1 4.10 60 0-20Mph 2 4.17 61Drive Trim 100% dn 3 5.00 74 Avg 4.42 65 Recommended Propeller Yes ______________________________________
TABLE 4A
______________________________________
BOAT TEST REPORT
MARINE ENGINE FUEL INJECTION
TEST NUMBER: Test 1
Normal Hull
______________________________________
1000 RPM ZERO LIST
______________________________________
slip %
48.4% 1 7.7 mph 83 DB
mpg 1.99 2 6.6 mph 4.25 BPA
trim 100% DN 3 7.2 mph 3.6 GPH
plates
None avg 7.2 mph 227 RANGE
______________________________________
1500 RPM ZERO LIST
______________________________________
slip %
55.4% 1 9.9 mph 85 DB
mpg 1.45 2 8.7 mph 6.5 BPA
trim 100% DN 3 9.3 mph 6.4 GPH
plates
None avg 9.3 mph 156 RANGE
______________________________________
2000 RPM ZERO LIST
______________________________________
slip %
66.4% 1 10.5 mph 86 DB
mpg 0.77 2 8.0 mph 7.75 BPA
trim 100% DN 3 9.5 mph 12.2 GPH
plates
None avg 9.3 mph 87 RANGE
______________________________________
2500 RPM ZERO LIST
______________________________________
slip %
21.4% 1 27.0 mph 87 DB
mpg 1.72 2 27.6 mph 3.75 BPA
trim 100% DN 3 27.3 mph 15.9 GPH
plates
None avg 27.3 mph 196 RANGE
______________________________________
3000 RPM ZERO LIST
______________________________________
slip %
20.8% 1 32.6 mph 88 DB
mpg 1.73 2 33.4 mph 3.75 BPA
trim 20% UP 3 33.0 mph 19.1 GPH
plates
None avg 33.0 mph 197 RANGE
______________________________________
3500 Cruise RPM ZERO LIST
______________________________________
slip %
15.5% 1 40.7 mph 90 DB
mpg 1.74 2 41.4 mph 3.50 BPA
trim 35% UP 3 41.1 mph 23.6 GPH
plates
None avg 41.1 mph 193 RANGE
______________________________________
3500 RPM ZERO LIST
______________________________________
slip %
15.5% 1 40.7 mph 90 DB
mpg 1.74 2 41.4 mph 3.50 BPA
trim 35% UP 3 41.1 mph 23.6 GPH
plates
None avg 41.1 mph 193 RANGE
______________________________________
4000 RPM ZERO LIST
______________________________________
slip %
14.7% 1 47.8 mph 91 DB
mpg 1.51 2 47.0 mph 3.25 BPA
trim 60% UP 3 47.4 mph 31.4 GPH
plates
None avg 47.4 mph 172 RANGE
______________________________________
4500 RPM ZERO LIST
______________________________________
slip %
14.5% 1 54.0 mph 95 DB
mpg 1.35 2 53.4 mph 3.00 BPA
trim 70% UP 3 53.0 mph 39.5 GPH
plates
None avg 53.5 mph 154 RANGE
______________________________________
4760 MAX RPM ZERO LIST
______________________________________
slip %
14.3% 1 56.0 mph 97 DB
mpg 1.22 2 57.2 mph 3.00 BPA
trim 80% UP 3 56.8 mph 46.6 GPH
plates
None avg 56.7 mph 139 RANGE
______________________________________
*PHS = Polyhydroxysterene
4750 RPM STBD ENGINE
4820 RPM PORT ENGINE
0 RPM SINGLE ENGINE
TABLE 4B
______________________________________
BOAT TEST REPORT
MARINE ENGINE FUEL INJECTION
TEST NUMBER: Test 2
Hull Coated with PHS
______________________________________
1000 RPM ZERO LIST
______________________________________
slip %
48.2% 1 7.6 mph 83 DB
mpg 2.06 2 6.8 mph 4.25 BPA
trim 100% DN 3 7.2 mph 3.5 GPH
plates
None avg 7.2 mph 235 RANGE
______________________________________
1500 RPM ZERO LIST
______________________________________
slip %
52.5% 1 9.7 mph 85 DB
mpg 1.52 2 10.1 mph 7.00 BPA
trim 100% DN 3 9.9 mph 8.5 GPH
plates
None avg 9.9 mph 174 RANGE
______________________________________
2000 RPM ZERO LIST
______________________________________
slip %
61.2% 1 10.0 mph 86 DB
mpg .90 2 11.5 mph 8.25 BPA
trim 100% DN 3 10.8 mph 12.0 GPH
plates
None avg 10.8 mph 102 RANGE
______________________________________
2500 RPM ZERO LIST
______________________________________
slip %
15.1% 1 29.2 mph 87 DB
mpg 1.84 2 29.7 mph 4.25 BPA
trim 100% DN 3 29.5 mph 16.0 GPH
plates
None avg 29.5 mph 210 RANGE
______________________________________
3000 RPM ZERO LIST
______________________________________
slip %
14.1% 1 36.0 mph 88 DB
mpg 1.85 2 36.4 mph 4.00 BPA
trim 20% UP 3 35.0 mph 19.3 GPH
plates
None avg 35.8 mph 211 RANGE
______________________________________
3500 Cruise RPM ZERO LIST
______________________________________
slip %
13.6% 1 42.1 mph 90 DB
mpg 1.79 2 42.6 mph 3.50 BPA
trim 35% UP 3 41.3 mph 23.5 GPH
plates
None avg 42.0 mph 204 RANGE
______________________________________
3500 RPM ZERO LIST
______________________________________
slip %
13.6% 1 42.1 mph 90 DB
mpg 1.79 2 42.6 mph 3.50 BPA
trim 35% UP 3 41.3 mph 23.5 GPH
plates
None avg 42.0 mph 204 RANGE
______________________________________
4000 RPM ZERO LIST
______________________________________
slip %
12.5% 1 49.0 91 DB
mpg 1.54 2 48.7 mph 3.50 BPA
trim 60% UP 3 48.1 mph 31.5 GPH
plates
None avg 48.6 mph 176 RANGE
______________________________________
4500 RPM ZERO LIST
______________________________________
slip %
12.4% 1 55.0 mph 95 DB
mpg 1.37 2 54.5 mph 3.50 BPA
trim 70% UP 3 54.8 mph 40.1 GPH
plates
None avg 54.8 mph 156 RANGE
______________________________________
4785 MAX RPM ZERO LIST
______________________________________
slip %
12.4% 1 58.0 mph 97 DB
mpg 1.25 2 58.2 mph 3.25 BPA
trim 80% UP 3 58.5 mph 46.5 GPH
plates
None avg 58.2 mph 143 RANGE
______________________________________
*PHS = Polyhydroxysterene
4750 RPM STBD ENGINE
4820 RPM PORT ENGINE
0 RPM SINGLE ENGINE
TABLE 5
__________________________________________________________________________
SO-BRIGHT INTERNATIONAL TEST RESULTS
Test One - Prior to Chemical Application
Test Two - After Chemical Application
TEST NR
Test 1
Test 2
Changes
Test 1
Test 2
Changes
Test 1
Test 2
Changes
__________________________________________________________________________
20 Nova Spyder
RPM MPH MPH IN MPH
MPG MPG IN MPG
RANGE
RANGE
IN RANGE
Mercruiser
1000 7.2 7.2 0.0 2.0 2.1 0.07 227 235 7.6
350 Magnum
1500 9.3 9.9 0.6 1.5 1.5 0.07 166 174 8.0
Alpha One
2000 9.3 10.8
1.4 0.8 0.9 0.13 87 102 15.1
Sarasota Bay
2500 27.3
29.5
2.2 1.7 1.8 0.12 196 210 14.2
Quicksilver
3000 33.0
35.8
2.8 1.7 1.9 0.13 197 211 14.5
Stainless Steel
3500 41.1
42.0
0.9 1.7 1.8 0.05 #8 204 5.4
Three Blades
4000 47.4
48.6
1.2 1.5 1.5 0.03 172 176 3.8
RH(2)
21" 4500 53.5
54.8
1.3 1.4 1.4 0.03 154 158 3.8
4760 4785 56.7
58.2
1.6 1.2 1.3 0.04 121 124 3.6
ACCELERATION (0-20 MPH):
Test 1
Test 2
SECONDS TO PLANE:
4.4 3.9
FEET TO PLANE: 65.0 57.0
__________________________________________________________________________
Notes:
The purpose of this test was to demonstrate the improvements we found (if
any) in the performance of the boat described above. To do this we tested
the boat prior to and immediately after a chemical application to the
boats hull bottom. Test 1 shows results prior to and Test 2 shows results
after.
The results clearly show that a boat coated with the composition of the present invention moves faster than an uncoated boat under substantially identical power consumption; similarly, for the same speed the coating reduces the rate of fuel consumption or increase the distance the boat will travel on a full tank of fuel. The difference varies with speed or power of the boat, and Table 5 shows that in the tests the maximum improvement of 17% at 2000 rpm corresponded to 10.8 miles/hour. At higher speeds the boat started to plane, resulting in less boat surface area in contact with water, and therefore a reduced beneficial effect of the coating is observed. For the case of ocean liners, cargo boats, or sailboats, which do not plane, it is expected that the beneficial effects of the coating of the present invention would continue to increase with an increase in power and speed since the surface-to-water contact area would not change under these changing conditions.
Therefore, it can be seen that the composition and methods of the present invention represent a significant increase in speed and fuel efficiency, thus conferring concomitant ecological and economic benefits.
It may be appreciated by one skilled in the art that additional embodiments may be contemplated, including analogous compositions having similar hyrophilic polymeric elements.
In the foregoing description, certain terms have been used for brevity, clarity, and understanding, but no unnecessary limitations are to be implied therefrom beyond the requirements of the prior art, because such words are used for description purposes herein and are intended to be broadly construed. Moreover, the embodiments of the apparatus illustrated and described herein are by way of example, and the scope of the invention is not limited to the exact details of construction.
Having now described the invention, the construction, the operation and use of preferred embodiment thereof, and the advantageous new and useful results obtained thereby, the new and useful constructions, and reasonable mechanical equivalents thereof obvious to those skilled in the art, are set forth in the appended claims.
Claims (13)
1. A method for coating a marine watercraft comprising the step of applying a hydrophilic composition comprising a polyhydroxystyrene of the novolak type to an outer surface of the watercraft.
2. The method recited in claim 1, wherein the composition comprises the polyhydroxystyrene copolymerized with a second hydrophilic polymer to form a water-insoluble, alcohol-soluble copolymer.
3. The method recited in claim 2, wherein the second hydrophilic polymer is selected from the group consisting of polyhydroxyethyl methacrylate, polyallylamine, polyaminostyrene, polyacrylamide, polyacrylic acid, and polyhydroxymethylene.
4. The method recited in claim 1, further comprising an antifouling agent.
5. The method recited in claim 4, wherein the antifouling agent comprises at least one compound selected from the group consisting of copper powder, copper oxide, zinc oxide, titanium oxide, and tin oxide.
6. The method recited in claim 1, wherein the composition comprises the polyhydroxystyrene in a low-molecular-weight oxygenated hydrocarbon solvent, the polyhydroxystyrene present in a solution in a concentration range of 5-20 wt/vol %.
7. The method recited in claim 6, wherein the solvent is selected from a group consisting of an alcohol and a ketone.
8. The method recited in claim 7, wherein the solvent comprises methanol.
9. The method recited in claim 6, wherein the composition further comprises an antifouling agent in a concentration range of 5-20 wt/vol %.
10. The method recited in claim 1, further comprising a pigment.
11. A method for increasing a kinematic efficiency of a marine watercraft during motion through an aqueous medium comprising the step of applying a coating to a submersible surface of the watercraft, the coating comprising a hydrophilic composition including a polyhydroxystyrene of the novolak type.
12. The method recited in claim 11, wherein the coating further comprises an antifouling agent and a pigment.
13. The method recited in claim 11, further comprising the step, following the applying step, of permitting the coating to dry prior to exposing the watercraft to an aqueous environment.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/238,818 US6045869A (en) | 1999-01-28 | 1999-01-28 | Water-insoluble hydrophilic marine coating and methods |
| US09/890,089 US6537609B1 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
| CA002360176A CA2360176C (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
| EP99973653A EP1163300A1 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
| JP2000596083A JP4394837B2 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine paint and method |
| KR1020017009549A KR100637684B1 (en) | 1999-01-28 | 1999-10-25 | Insoluble Hydrophilic Marine Coatings |
| CNB998163910A CN1165587C (en) | 1999-01-28 | 1999-10-25 | Water insoluble hydrophilic marine coatings and methods |
| PCT/US1999/024048 WO2000044835A1 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
| AU12056/00A AU1205600A (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
| US10/123,536 US6706784B2 (en) | 1999-01-28 | 2002-04-16 | Water-insoluble hydrophilic surface coating and methods |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/238,818 US6045869A (en) | 1999-01-28 | 1999-01-28 | Water-insoluble hydrophilic marine coating and methods |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1999/024048 Continuation-In-Part WO2000044835A1 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/890,089 Continuation-In-Part US6537609B1 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
| US09/542,756 Continuation-In-Part US6372028B1 (en) | 1999-01-28 | 2000-04-04 | Water-insoluble hydrophilic surface coating and methods |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US6045869A true US6045869A (en) | 2000-04-04 |
Family
ID=22899454
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/238,818 Expired - Lifetime US6045869A (en) | 1999-01-28 | 1999-01-28 | Water-insoluble hydrophilic marine coating and methods |
| US09/890,089 Expired - Lifetime US6537609B1 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/890,089 Expired - Lifetime US6537609B1 (en) | 1999-01-28 | 1999-10-25 | Water-insoluble hydrophilic marine coating and methods |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US6045869A (en) |
| EP (1) | EP1163300A1 (en) |
| JP (1) | JP4394837B2 (en) |
| KR (1) | KR100637684B1 (en) |
| CN (1) | CN1165587C (en) |
| AU (1) | AU1205600A (en) |
| CA (1) | CA2360176C (en) |
| WO (1) | WO2000044835A1 (en) |
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| US6313193B1 (en) | 2000-06-02 | 2001-11-06 | Microphase Coatings Inc. | Antifouling coating composition |
| US6476095B2 (en) | 2000-06-02 | 2002-11-05 | Microphase Coatings, Inc. | Antifouling coating composition |
| US6559201B2 (en) | 2000-06-02 | 2003-05-06 | Microphase Coatings, Inc. | Antifouling coating composition |
| US6702953B2 (en) | 2000-12-14 | 2004-03-09 | Microphase Coatings, Inc. | Anti-icing composition |
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| US20050282953A1 (en) * | 2004-06-17 | 2005-12-22 | Microphase Coatings, Inc. | Hydrophobic coating composition |
| US20060110612A1 (en) * | 2003-04-10 | 2006-05-25 | Microphase Coatings, Inc. | Thermal barrier composition |
| US20060210807A1 (en) * | 2005-03-11 | 2006-09-21 | Microphase Coatings, Inc. | Antifouling coating composition |
| WO2006119628A1 (en) | 2005-05-10 | 2006-11-16 | Gesser Hyman D | Irrigation system and associated methods |
| US7163750B2 (en) | 2003-04-10 | 2007-01-16 | Microphase Coatings, Inc. | Thermal barrier composition |
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| WO2003008505A2 (en) * | 2001-07-17 | 2003-01-30 | Foster-Miller, Inc. | A method of preparing an anti-fouling coating |
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- 1999-10-25 US US09/890,089 patent/US6537609B1/en not_active Expired - Lifetime
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- 1999-10-25 WO PCT/US1999/024048 patent/WO2000044835A1/en active IP Right Grant
- 1999-10-25 KR KR1020017009549A patent/KR100637684B1/en not_active IP Right Cessation
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| US20040094049A1 (en) * | 1999-12-07 | 2004-05-20 | Fuji Photo Film Co., Ltd. | Goods-wrapping apparatus including a printer |
| US20040093830A1 (en) * | 1999-12-07 | 2004-05-20 | Fuji Photo Film Co., Ltd. | Goods-wrapping apparatus including a printer |
| US6476095B2 (en) | 2000-06-02 | 2002-11-05 | Microphase Coatings, Inc. | Antifouling coating composition |
| US6559201B2 (en) | 2000-06-02 | 2003-05-06 | Microphase Coatings, Inc. | Antifouling coating composition |
| US6313193B1 (en) | 2000-06-02 | 2001-11-06 | Microphase Coatings Inc. | Antifouling coating composition |
| US6702953B2 (en) | 2000-12-14 | 2004-03-09 | Microphase Coatings, Inc. | Anti-icing composition |
| US7163750B2 (en) | 2003-04-10 | 2007-01-16 | Microphase Coatings, Inc. | Thermal barrier composition |
| US20060110612A1 (en) * | 2003-04-10 | 2006-05-25 | Microphase Coatings, Inc. | Thermal barrier composition |
| US7687150B2 (en) | 2003-04-10 | 2010-03-30 | Microphase Coatings, Inc. | Thermal barrier composition |
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| US20060210807A1 (en) * | 2005-03-11 | 2006-09-21 | Microphase Coatings, Inc. | Antifouling coating composition |
| WO2006119628A1 (en) | 2005-05-10 | 2006-11-16 | Gesser Hyman D | Irrigation system and associated methods |
| US20090130160A1 (en) * | 2007-11-21 | 2009-05-21 | Fiber Innovation Technology, Inc. | Fiber for wound dressing |
| US20090294724A1 (en) * | 2008-05-27 | 2009-12-03 | Appealing Products, Inc. | Anti-icing material and surface treatments |
| US20110179705A1 (en) * | 2010-01-25 | 2011-07-28 | Developmental Technologies, Llc | Multi-Chamber Line And System For Plant Irrigation And Fertigation And Associated Methods |
| US8312671B2 (en) * | 2010-01-25 | 2012-11-20 | Developmental Technologies, Llc | Multi-chamber line and system for plant irrigation and fertigation and associated methods |
| US20140318433A1 (en) * | 2011-12-02 | 2014-10-30 | Akzo Nobel Coatings International B.V. | Waterborne antifouling coating composition |
| US9290669B2 (en) * | 2011-12-02 | 2016-03-22 | Akzo Nobel Coatings International B.V. | Waterborne antifouling coating composition |
| US12012981B2 (en) * | 2013-03-12 | 2024-06-18 | Texas Tech University System | Surface coating for reduction of aerodynamic noise and vibrations |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4394837B2 (en) | 2010-01-06 |
| CA2360176C (en) | 2005-09-20 |
| KR20020001727A (en) | 2002-01-09 |
| WO2000044835A1 (en) | 2000-08-03 |
| CA2360176A1 (en) | 2000-08-03 |
| CN1344299A (en) | 2002-04-10 |
| JP2002535142A (en) | 2002-10-22 |
| KR100637684B1 (en) | 2006-10-24 |
| EP1163300A1 (en) | 2001-12-19 |
| AU1205600A (en) | 2000-08-18 |
| CN1165587C (en) | 2004-09-08 |
| US6537609B1 (en) | 2003-03-25 |
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